Quantification of Organic Porosity and Water Accessibility in Marcellus Shale Using Neutron Scattering

Gu, Xin; Mildner, David F.  R.; Cole, David R.; Rother, Gernot; Slingerland, Rudy; Brantley, Susan L.

doi:10.1021/acs.energyfuels.5b02878

Quantification of Organic Porosity and Water Accessibility in Marcellus Shale Using Neutron Scattering

Journal Article · Thu Apr 28 00:00:00 EDT 2016 · Energy and Fuels

DOI:https://doi.org/10.1021/acs.energyfuels.5b02878· OSTI ID:1319207

Gu, Xin ^[1]; Mildner, David F. R. ^[2]; Cole, David R. ^[3]; Rother, Gernot ^[4]; Slingerland, Rudy ^[1]; Brantley, Susan L. ^[5]

Pennsylvania State Univ., University Park, PA (United States). Dept. of Geosciences
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
The Ohio State Univ., Columbus, OH (United States). School of Earth Sciences
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Pennsylvania State Univ., University Park, PA (United States). Dept. of Geosciences; Pennsylvania State Univ., University Park, PA (United States). Earth and Environmental Systems Inst.

Pores within organic matter (OM) are a significant contributor to the total pore system in gas shales. These pores contribute most of the storage capacity in gas shales. Here we present a novel approach to characterize the OM pore structure (including the porosity, specific surface area, pore size distribution, and water accessibility) in Marcellus shale. By using ultrasmall and small-angle neutron scattering, and by exploiting the contrast matching of the shale matrix with suitable mixtures of deuterated and protonated water, both total and water-accessible porosity were measured on centimeter-sized samples from two boreholes from the nanometer to micrometer scale with good statistical coverage. Samples were also measured after combustion at 450 °C. Analysis of scattering data from these procedures allowed quantification of OM porosity and water accessibility. OM hosts 24–47% of the total porosity for both organic-rich and -poor samples. This porosity occupies as much as 29% of the OM volume. In contrast to the current paradigm in the literature that OM porosity is organophilic and therefore not likely to contain water, our results demonstrate that OM pores with widths >20 nm exhibit the characteristics of water accessibility. In conclusion, our approach reveals the complex structure and wetting behavior of the OM porosity at scales that are hard to interrogate using other techniques.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Nanoscale Control of Geologic CO2 (NCGC); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1319207

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels Journal Issue: 6 Vol. 30; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (58)

Chemical modelling of kerogens Behar, F.; Vandenbroucke, M. Organic Geochemistry, Vol. 11, Issue 1 https://doi.org/10.1016/0146-6380(87)90047-7	journal	January 1987
Apatite fission-track thermochronology of the Pennsylvania Appalachian Basin Roden, Mary K.; Miller, Donald S. Geomorphology, Vol. 2, Issue 1-3 https://doi.org/10.1016/0169-555X(89)90005-6	journal	September 1989
Small angle neutron scattering signature of oil generation in artificially and naturally matured hydrocarbon source rocks Radliński, A. P.; Boreham, C. J.; Lindner, P. Organic Geochemistry, Vol. 31, Issue 1 https://doi.org/10.1016/S0146-6380(99)00128-X	journal	January 2000
Evolution of porosity and geochemistry in Marcellus Formation black shale during weathering Jin, Lixin; Mathur, Ryan; Rother, Gernot Chemical Geology, Vol. 356 https://doi.org/10.1016/j.chemgeo.2013.07.012	journal	October 2013
The nature of porosity in organic-rich mudstones of the Upper Jurassic Kimmeridge Clay Formation, North Sea, offshore United Kingdom Fishman, Neil S.; Hackley, Paul C.; Lowers, Heather A. International Journal of Coal Geology, Vol. 103 https://doi.org/10.1016/j.coal.2012.07.012	journal	December 2012
Molecular simulation of methane adsorption in micro- and mesoporous carbons with applications to coal and gas shale systems Mosher, Keith; He, Jiajun; Liu, Yangyang International Journal of Coal Geology, Vol. 109-110 https://doi.org/10.1016/j.coal.2013.01.001	journal	April 2013
Pore structure characterization of North American shale gas reservoirs using USANS/SANS, gas adsorption, and mercury intrusion Clarkson, C. R.; Solano, N.; Bustin, R. M. Fuel, Vol. 103 https://doi.org/10.1016/j.fuel.2012.06.119	journal	January 2013
The neutron scattering length density of kerogen and coal as determined by CH3OH/CD3OH exchange Thomas, Jeffrey J.; Valenza, John J.; Craddock, Paul R. Fuel, Vol. 117 https://doi.org/10.1016/j.fuel.2013.09.075	journal	January 2014
Nano-scale texture and porosity of organic matter and clay minerals in organic-rich mudrocks Kuila, Utpalendu; McCarty, Douglas K.; Derkowski, Arkadiusz Fuel, Vol. 135 https://doi.org/10.1016/j.fuel.2014.06.036	journal	November 2014
Protection of organic carbon in soil microaggregates via restructuring of aggregate porosity and filling of pores with accumulating organic matter McCarthy, John F.; Ilavsky, Jan; Jastrow, Julie D. Geochimica et Cosmochimica Acta, Vol. 72, Issue 19 https://doi.org/10.1016/j.gca.2008.06.015	journal	October 2008
Angstrom-to-millimeter characterization of sedimentary rock microstructure Radlinski, A. P.; Ioannidis, M. A.; Hinde, A. L. Journal of Colloid and Interface Science, Vol. 274, Issue 2 https://doi.org/10.1016/j.jcis.2004.02.035	journal	June 2004
Geochemical evolution of organic-rich shales with increasing maturity: A STXM and TEM study of the Posidonia Shale (Lower Toarcian, northern Germany) Bernard, Sylvain; Horsfield, Brian; Schulz, Hans-Martin Marine and Petroleum Geology, Vol. 31, Issue 1 https://doi.org/10.1016/j.marpetgeo.2011.05.010	journal	March 2012
Quantitative evaluation of TOC, organic porosity and gas retention distribution in a gas shale play using petroleum system modeling: Application to the Mississippian Barnett Shale Romero-Sarmiento, Maria-Fernanda; Ducros, Mathieu; Carpentier, Bernard Marine and Petroleum Geology, Vol. 45 https://doi.org/10.1016/j.marpetgeo.2013.04.003	journal	August 2013
Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems Zhang, Tongwei; Ellis, Geoffrey S.; Ruppel, Stephen C. Organic Geochemistry, Vol. 47 https://doi.org/10.1016/j.orggeochem.2012.03.012	journal	June 2012
Is organic pore development in gas shales influenced by the primary porosity and structure of thermally immature organic matter? Löhr, S. C.; Baruch, E. T.; Hall, P. A. Organic Geochemistry, Vol. 87 https://doi.org/10.1016/j.orggeochem.2015.07.010	journal	October 2015
Pores in Marcellus Shale: A Neutron Scattering and FIB-SEM Study Gu, Xin; Cole, David R.; Rother, Gernot Energy & Fuels, Vol. 29, Issue 3 https://doi.org/10.1021/acs.energyfuels.5b00033	journal	February 2015
Porosity of Coal and Shale: Insights from Gas Adsorption and SANS/USANS Techniques Mastalerz, Maria; He, Lilin; Melnichenko, Yuri B. Energy & Fuels, Vol. 26, Issue 8 https://doi.org/10.1021/ef300735t	journal	July 2012
A USANS/SANS Study of the Accessibility of Pores in the Barnett Shale to Methane and Water Ruppert, Leslie F.; Sakurovs, Richard; Blach, Tomasz P. Energy & Fuels, Vol. 27, Issue 2 https://doi.org/10.1021/ef301859s	journal	February 2013
Spontaneous Imbibition of Brine and Oil in Gas Shales: Effect of Water Adsorption and Resulting Microfractures Dehghanpour, H.; Lan, Q.; Saeed, Y. Energy & Fuels, Vol. 27, Issue 6 https://doi.org/10.1021/ef4002814	journal	May 2013
Methane Adsorption on Shale under Simulated Geological Temperature and Pressure Conditions Rexer, Thomas F. T.; Benham, Michael J.; Aplin, Andrew C. Energy & Fuels, Vol. 27, Issue 6 https://doi.org/10.1021/ef400381v	journal	May 2013
Pore Architecture and Connectivity in Gas Shale King, Hubert E.; Eberle, Aaron P. R.; Walters, Clifford C. Energy & Fuels, Vol. 29, Issue 3 https://doi.org/10.1021/ef502402e	journal	February 2015
Effect of Temperature on the Adsorption of Water in Porous Carbons Striolo, A.; Gubbins, K. E.; Gruszkiewicz, M. S. Langmuir, Vol. 21, Issue 21 https://doi.org/10.1021/la051120t	journal	October 2005
Post-Alleghanian unroofing history of the Appalachian Basin, Pennsylvania, from apatite fission track analysis and thermal models Blackmer, Gale C.; Omar, Gomaa I.; Gold, David P. Tectonics, Vol. 13, Issue 5 https://doi.org/10.1029/94TC01507	journal	October 1994
Small‐angle scattering of shaley rocks with fractal pore interfaces Mildner, D. F. R.; Rezvani, R.; Hall, P. L. Applied Physics Letters, Vol. 48, Issue 19 https://doi.org/10.1063/1.96964	journal	May 1986
Capillary tension and imbibition sequester frack fluid in Marcellus gas shale Engelder, T. Proceedings of the National Academy of Sciences, Vol. 109, Issue 52 https://doi.org/10.1073/pnas.1216133110	journal	December 2012
Small-angle scattering from porous solids with fractal geometry Mildner, D. F. R.; Hall, P. L. Journal of Physics D: Applied Physics, Vol. 19, Issue 8 https://doi.org/10.1088/0022-3727/19/8/021	journal	August 1986
PRINSAS – a Windows-based computer program for the processing and interpretation of small-angle scattering data tailored to the analysis of sedimentary rocks Hinde, Alan L. Journal of Applied Crystallography, Vol. 37, Issue 6 https://doi.org/10.1107/S0021889804021260	journal	November 2004
Design and performance of a thermal-neutron double-crystal diffractometer for USANS at NIST Barker, J. G.; Glinka, C. J.; Moyer, J. J. Journal of Applied Crystallography, Vol. 38, Issue 6, p. 1004-1011 https://doi.org/10.1107/S0021889805032103	journal	November 2005
Reduction and analysis of SANS and USANS data using IGOR Pro Kline, Steven R. Journal of Applied Crystallography, Vol. 39, Issue 6, p. 895-900 https://doi.org/10.1107/S0021889806035059	journal	November 2006
Small-angle scattering studies of disordered, porous and fractal systems Schmidt, P. W. Journal of Applied Crystallography, Vol. 24, Issue 5 https://doi.org/10.1107/S0021889891003400	journal	October 1991
DEMUX/MUX: removal of multiple scattering from small-angle data Monkenbusch, M. Journal of Applied Crystallography, Vol. 24, Issue 5 https://doi.org/10.1107/S0021889891005277	journal	October 1991
The 30 m Small-Angle Neutron Scattering Instruments at the National Institute of Standards and Technology Glinka, C. J.; Barker, J. G.; Hammouda, B. Journal of Applied Crystallography, Vol. 31, Issue 3, p. 430-445 https://doi.org/10.1107/S0021889897017020	journal	June 1998
Specific surface area and pore-size distribution in clays and shales Kuila, Utpalendu; Prasad, Manika Geophysical Prospecting, Vol. 61, Issue 2 https://doi.org/10.1111/1365-2478.12028	journal	January 2013
Impact of Shale Gas Development on Regional Water Quality Vidic, R. D.; Brantley, S. L.; Vandenbossche, J. M. Science, Vol. 340, Issue 6134 https://doi.org/10.1126/science.1235009	journal	May 2013
Geochemical controls on shale microstructure Valenza, John J.; Drenzek, Nicholas; Marques, Flora Geology, Vol. 41, Issue 5 https://doi.org/10.1130/G33639.1	journal	May 2013
Pore types in the Barnett and Woodford gas shales: Contribution to understanding gas storage and migration pathways in fine-grained rocks Slatt, Roger M.; O'Brien, Neal R. AAPG Bulletin, Vol. 95, Issue 12 https://doi.org/10.1306/03301110145	journal	December 2011
A model describing flowback chemistry changes with time after Marcellus Shale hydraulic fracturing Balashov, Victor N.; Engelder, Terry; Gu, Xin AAPG Bulletin, Vol. 99, Issue 01 https://doi.org/10.1306/06041413119	journal	January 2015
Organic matter-hosted pore system, Marcellus Formation (Devonian), Pennsylvania Milliken, Kitty L.; Rudnicki, Mark; Awwiller, David N. AAPG Bulletin, Vol. 97, Issue 2 https://doi.org/10.1306/07231212048	journal	February 2013
Microstructural investigation of gas shales in two and three dimensions using nanometer-scale resolution imaging Curtis, Mark E.; Sondergeld, Carl H.; Ambrose, Raymond J. AAPG Bulletin, Vol. 96, Issue 4 https://doi.org/10.1306/08151110188	journal	April 2012
Spectrum of pore types and networks in mudrocks and a descriptive classification for matrix-related mudrock pores Loucks, Robert G.; Reed, Robert M.; Ruppel, Stephen C. AAPG Bulletin, Vol. 96, Issue 6 https://doi.org/10.1306/08171111061	journal	June 2012
Organic matter pores and oil generation in the Tuscaloosa marine shale Lu, Jiemin; Ruppel, Stephen C.; Rowe, Harry D. AAPG Bulletin, Vol. 99, Issue 02 https://doi.org/10.1306/08201414055	journal	February 2015
Sequence stratigraphy and depositional environments of the Shamokin (Union Springs) Member, Marcellus Formation, and associated strata in the middle Appalachian Basin Kohl, Daniel; Slingerland, Rudy; Arthur, Mike AAPG Bulletin, Vol. 98, Issue 3 https://doi.org/10.1306/08231312124	journal	March 2014
Characterization of gas shale pore systems by porosimetry, pycnometry, surface area, and field emission scanning electron microscopy/transmission electron microscopy image analyses: Examples from the Barnett, Woodford, Haynesville, Marcellus, and Doig units Chalmers, Gareth R.; Bustin, R. Marc; Power, Ian M. AAPG Bulletin, Vol. 96, Issue 6 https://doi.org/10.1306/10171111052	journal	June 2012
Unconventional shale-gas systems: The Mississippian Barnett Shale of north-central Texas as one model for thermogenic shale-gas assessment Jarvie, Daniel M.; Hill, Ronald J.; Ruble, Tim E. AAPG Bulletin, Vol. 91, Issue 4 https://doi.org/10.1306/12190606068	journal	April 2007
Morphology, Genesis, and Distribution of Nanometer-Scale Pores in Siliceous Mudstones of the Mississippian Barnett Shale Loucks, R. G.; Reed, R. M.; Ruppel, S. C. Journal of Sedimentary Research, Vol. 79, Issue 12 https://doi.org/10.2110/jsr.2009.092	journal	November 2009
Nanoscale Gas Flow in Shale Gas Sediments Javadpour, F.; Fisher, D.; Unsworth, M. Journal of Canadian Petroleum Technology, Vol. 46, Issue 10 https://doi.org/10.2118/07-10-06	journal	October 2007
Pore Networks and Fluid Flow in Gas Shales Wang, Fred P.; Reed, Rob M. SPE Annual Technical Conference and Exhibition https://doi.org/10.2118/124253-MS	conference	April 2013
From Oil-Prone Source Rock to Gas-Producing Shale Reservoir - Geologic and Petrophysical Characterization of Unconventional Shale Gas Reservoirs Passey, Quinn R.; Bohacs, Kevin; Esch, William Lee International Oil and Gas Conference and Exhibition in China https://doi.org/10.2118/131350-MS	conference	April 2013
Kerogen Density in the Marcellus Shale Ward, John SPE Unconventional Gas Conference https://doi.org/10.2118/131767-MS	conference	April 2013
New Pore-scale Considerations for Shale Gas in Place Calculations Ambrose, Raymond Joseph; Hartman, Robert Chad; Diaz Campos, Mery SPE Unconventional Gas Conference https://doi.org/10.2118/131772-MS	conference	April 2013
Transmission and Scanning Electron Microscopy Investigation of Pore Connectivity of Gas Shales on the Nanoscale Curtis, Mark Erman; Ambrose, Raymond Joseph; Sondergeld, Carl H. North American Unconventional Gas Conference and Exhibition https://doi.org/10.2118/144391-MS	conference	April 2013
Multiscale Gas Transport in Shales With Local Kerogen Heterogeneities Akkutlu, I. Yucel; Fathi, Ebrahim SPE Journal, Vol. 17, Issue 04 https://doi.org/10.2118/146422-PA	journal	December 2012
NMR Study of Shale Wettability Odusina, Elijah O.; Sondergeld, Carl H.; Rai, Chandra Shekhar Canadian Unconventional Resources Conference https://doi.org/10.2118/147371-MS	conference	April 2013
Microscopic Dynamics of Water and Hydrocarbon in Shale-Kerogen Pores of Potentially Mixed Wettability Hu, Yinan; Devegowda, Deepak; Striolo, Alberto SPE Journal, Vol. 20, Issue 01 https://doi.org/10.2118/167234-PA	journal	February 2014
Characterization of deep weathering and nanoporosity development in shale--A neutron study Jin, L.; Rother, G.; Cole, D. R. American Mineralogist, Vol. 96, Issue 4 https://doi.org/10.2138/am.2011.3598	journal	March 2011
Small-Angle Neutron Scattering and the Microstructure of Rocks Radlinski, A. P. Reviews in Mineralogy and Geochemistry, Vol. 63, Issue 1 https://doi.org/10.2138/rmg.2006.63.14	journal	January 2006
Characterization and Analysis of Porosity and Pore Structures Anovitz, Lawrence M.; Cole, David R. Reviews in Mineralogy and Geochemistry, Vol. 80, Issue 1 https://doi.org/10.2138/rmg.2015.80.04	journal	January 2015
Thermal Maturity Patterns (CAI and %Ro) in Upper Ordovician and Devonian Rocks of the Appalachian Basin: A Major Revision of USGS Map I-917-E Using New Subsurface Collections Repetski, John E.; Ryder, Robert T.; Weary, David J. https://doi.org/10.3133/sim3006	report	January 2008

Cited By (7)

Integrating SANS and fluid-invasion methods to characterize pore structure of typical American shale oil reservoirs Zhao, Jianhua; Jin, Zhijun; Hu, Qinhong Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-15362-0	journal	November 2017
An analytical equation for oil transport in nanopores of oil shale considering viscosity distribution Sun, Fengrui; Yao, Yuedong; Li, Xiangfang Journal of Petroleum Exploration and Production Technology, Vol. 9, Issue 1 https://doi.org/10.1007/s13202-018-0486-8	journal	June 2018
Supercritical CO ₂ -induced atomistic lubrication for water flow in a rough hydrophilic nanochannel Ho, Tuan A.; Wang, Yifeng; Ilgen, Anastasia Nanoscale, Vol. 10, Issue 42 https://doi.org/10.1039/c8nr06204h	journal	January 2018
Flow-through compression cell for small-angle and ultra-small-angle neutron scattering measurements Hjelm, Rex P.; Taylor, Mark A.; Frash, Luke P. Review of Scientific Instruments, Vol. 89, Issue 5 https://doi.org/10.1063/1.5022678	journal	May 2018
Determination of porosity in anisotropic fractal systems by neutron scattering Gu, Xin; Mildner, David F. R. Journal of Applied Crystallography, Vol. 51, Issue 1 https://doi.org/10.1107/s1600576718000080	journal	February 2018
Liquid Storage Characteristics of Nanoporous Particles in Shale: Rigorous Proof Cui, Jiangfeng; Cheng, Long Energies, Vol. 12, Issue 20 https://doi.org/10.3390/en12203985	journal	October 2019
Nano-Scale Pore Structure and Fractal Dimension of Longmaxi Shale in the Upper Yangtze Region, South China: A Case Study of the Laifeng–Xianfeng Block Using HIM and N2 Adsorption Huang, Cheng; Ju, Yiwen; Zhu, Hongjian Minerals, Vol. 9, Issue 6 https://doi.org/10.3390/min9060356	journal	June 2019

Similar Records

Pores in Marcellus Shale: A Neutron Scattering and FIB-SEM Study

Journal Article · Sun Jan 25 23:00:00 EST 2015 · Energy and Fuels · OSTI ID:1279416

Pore accessibility and trapping of methane in Marcellus shale

Journal Article · Mon Sep 13 20:00:00 EDT 2021 · International Journal of Coal Geology · OSTI ID:1827291

Accessibility of Pores to Methane in New Albany Shale Samples of Varying Maturity Determined Using SANS and USANS

Journal Article · Mon Dec 13 19:00:00 EST 2021 · Energies · OSTI ID:1835930

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
58 GEOSCIENCES

Quantification of Organic Porosity and Water Accessibility in Marcellus Shale Using Neutron Scattering

Citation Formats

References (58)

Cited By (7)

Similar Records

Related Subjects